CN104250362A - Low-hardness polyurethane elastomer and preparation method thereof - Google Patents

Low-hardness polyurethane elastomer and preparation method thereof Download PDF

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Publication number
CN104250362A
CN104250362A CN201410506802.XA CN201410506802A CN104250362A CN 104250362 A CN104250362 A CN 104250362A CN 201410506802 A CN201410506802 A CN 201410506802A CN 104250362 A CN104250362 A CN 104250362A
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polyurethane elastomer
polyester polyol
parts
mdi
acid
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刘山荣
刘殷良
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DONGGUAN HONES MATERIAL TECHNOLOGY Co Ltd
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DONGGUAN HONES MATERIAL TECHNOLOGY Co Ltd
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    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract

The invention relates to the technical field of polyurethane elastomers and in particular relates to a low-hardness polyurethane elastomer and a preparation method thereof. The polyurethane elastomer is prepared from the following components in parts by weight: 60-90 parts of polyester polyol, 10-25 parts of diisocyanate and 3-15 parts of a chain extender. The hardness of the low-hardness polyurethane elastomer is lower than 70A, and the low-hardness polyurethane elastomer has the advantages of high physical properties, reasonable cost and good convenience in production, does not contain hazardous substances, can effectively replace current toxic low-hardness PVC products, is good in transparency, and can also be widely used for various ejection devices. The preparation method is simple and mature, is high in production efficiency, and is beneficial to wide popularization and application.

Description

Polyurethane elastomer of a kind of soft and preparation method thereof
Technical field
The present invention relates to technical field of polyurethane elastomer, particularly relate to polyurethane elastomer of a kind of soft and preparation method thereof.
Background technology
Traditional polyurethane elastomer has good abrasion resistance, can keep flexibility, have excellent resistance to weather and chemical resistant properties etc., but current increasing market needs soft machinable polyurethane elastomer in very wide temperature range.Tradition is applied in the elastomerics of below shore hardness 70A mainly based on virose PVC, domestic commercial polyurethane elastomer hardness is many at shore hardness about 70A, therefore expects to have the polyurethane products that hardness is lower can replace tradition PVC product not environmentally always.Market demands are reached in order to make the pliability of urethane; at present mainly through add softening agent or with the blended preparation of other softer material to realize; but unfortunately; these methods can make the mechanical property of polyurethane product and physicals decline usually; even may cause environmental problem, and polyether(poly)urethane elastomerics due to hydrogen bond quantity few, physical property is poor; cause process of manufacture comparatively difficult, and raw materials cost is higher.For this reason, the above problems demand solves.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, and a kind of polyurethane elastomer can taking into account high physical property, reasonable cost and the advantage of convenient production, the effectively soft of the existing poisonous PVC product of replacement is provided.
Another object of the present invention is to for the deficiencies in the prior art, and a kind of method for preparing polyurethane elastic body of soft is provided.
The present invention is achieved through the following technical solutions.
A polyurethane elastomer for soft, it is made up of the raw material of following weight part:
Polyester polyol 60-90 part
Vulcabond 10-25 part
Chainextender 3-15 part;
Wherein, the hydroxyl value of polyester polyol is 28 ~ 150mgKOH/g, and acid number is 0.01 ~ 0.3mgK
OH/g, MW are 700 ~ 4000.
Preferably, a kind of polyurethane elastomer of soft, it is made up of the raw material of following weight part:
Polyester polyol 70-80 part
Vulcabond 15-20 part
Chainextender 6-12 part.
More preferred, a kind of polyurethane elastomer of soft, it is made up of the raw material of following weight part:
Polyester polyol 75 parts
Vulcabond 16 parts
Chainextender 9 parts.
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 1:0.9 ~ 1.5 through vacuum fusion method by any one in polyprotonic acid, polynary ester or both mixtures and polyvalent alcohol, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1 ~ 2h at 120 ~ 160 DEG C, then 180 ~ 250 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 28 ~ 150mgKOH/g, acid number is 0.01 ~ 0.3mgKOH/g, MW is 700 ~ 4000.
Wherein, polyvalent alcohol is any one or a few the mixture in glycol ether, butyleneglycol, propylene glycol, hexylene glycol, neopentyl glycol, 2-methyl propanediol, TriMethylolPropane(TMP), glycerine;
Polyprotonic acid is any one or a few the mixture in hexanodioic acid, terephthalic acid, m-phthalic acid;
Polynary ester is phthalic anhydride.
Wherein, vulcabond comprise 4,4-MDI, 2,4-MDI, extraordinary MDI, IPDI, PPDI, TMXDI, H 12any one or a few mixture in MDI, HDI, XDI, wherein, 4,4-MDI and 2,4-MDI that extraordinary MDI is 3-7 by weight ratio form.
Wherein, chainextender is ethylene glycol, propylene glycol, 1,3 butylene glycol, BDO, 2-methyl isophthalic acid, any one or a few the mixture in ammediol, hexylene glycol, 3-methyl 1,5-PD, 1,4 cyclohexane dimethanol.
The method for preparing polyurethane elastic body of above-mentioned soft, it comprises following preparation process:
A, by weight by polyester polyol, vulcabond, chainextender hybrid reaction, the temperature of reaction is 180-250 DEG C, obtained reactant;
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 140-200 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
Beneficial effect of the present invention is: the hardness of the polyurethane elastomer of soft of the present invention is lower than 70A, high physical property, reasonable cost and convenient advantage of producing can be taken into account, and do not contain hazardous substance, effectively can replace existing poisonous soft PVC product, and excellent transparency, multiple types injection equipment can also be widely used in.
Preparation method of the present invention is simple, and production efficiency is high, is conducive to popularity application.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
embodiment 1.
A, be the H of the polyester polyol of 60 parts, 7 parts 2,4-MDI, 8 parts by weight part 12mDI, the IPDI of 10 parts, the ethylene glycol of 1 part, the mixed with propylene glycol reaction of 2 parts, the temperature of reaction is 180 DEG C, obtained reactant;
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 0.9:1 through vacuum fusion method by glycol ether and hexanodioic acid, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 2h at 120 DEG C, then 180 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 28mgKOH/g, acid number is 0.3mgKOH/g, MW is 700;
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 140 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
embodiment 2.
The method for preparing polyurethane elastic body of the high rigidity of the present embodiment, it comprises following preparation process:
A, be the polyester polyol of 66 parts, the PPDI of 5 parts 4,4-MDI, 5 parts, the HDI of 10 parts, the 1,3 butylene glycol of 1 part, 2 parts 1 by weight part, 4-butyleneglycol, the 2-methyl isophthalic acid of 3 parts, ammediol hybrid reaction, the temperature of reaction is 200 DEG C, obtained reactant;
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 1.1:1 through vacuum fusion method by the mixture of the mixture of butyleneglycol, propylene glycol and terephthalic acid, m-phthalic acid, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1.8h at 130 DEG C, then 200 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 60mgKOH/g, acid number is 0.2mgKOH/g, MW is 1500;
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 155 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
embodiment 3.
The method for preparing polyurethane elastic body of the high rigidity of the present embodiment, it comprises following preparation process:
A, by weight part be 74 parts polyester polyol, 6 parts TMXDI, the XDI of 6 parts, the IPDI of 6 parts, the hexylene glycol of 3 parts, the 3-methyl 1 of 3 parts, 5-pentanediol, 3 parts 1,4-cyclohexanedimethanol hybrid reaction, the temperature of reaction is 215 DEG C, obtained reactant;
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 1.3:1 through vacuum fusion method by the mixture of the mixture of hexylene glycol, neopentyl glycol, 2-methyl propanediol and hexanodioic acid, terephthalic acid, m-phthalic acid, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1.6h at 140 DEG C, then 215 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 100mgKOH/g, acid number is 0.15mgKOH/g, MW is 2500.
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 170 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
embodiment 4.
The method for preparing polyurethane elastic body of the high rigidity of the present embodiment, it comprises following preparation process:
A, be the polyester polyol of 82 parts, the XDI of 6 parts, the H of 8 parts by weight part 12mDI, the propylene glycol of 5 parts, the 2-methyl isophthalic acid of 4 parts, ammediol, the 1,4 cyclohexane dimethanol hybrid reaction of 3 parts, the temperature of reaction is 230 DEG C, obtained reactant;
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 1.4:1 through vacuum fusion method by the mixture of the mixture of TriMethylolPropane(TMP), glycerine and terephthalic acid, phthalic anhydride, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1.4h at 150 DEG C, then 230 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 120mgKOH/g, acid number is 0.1mgKOH/g, MW is 3000.
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 185 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
embodiment 5.
The method for preparing polyurethane elastic body of the high rigidity of the present embodiment, it comprises following preparation process:
A, be ethylene glycol, the 1,3 butylene glycol of 5 parts, the 2-methyl isophthalic acid of 6 parts of 2,4-MDI, 4 parts of the polyester polyol of 90 parts, 4 parts 4,4-MDI, 6 parts by weight part, ammediol hybrid reaction, the temperature of reaction is 250 DEG C, obtained reactant;
Wherein, polyester polyol carries out dealcoholysis and dehydrating polycondensation form according to the molar ratio of 1.5:1 through vacuum fusion method by the mixture of butyleneglycol, neopentyl glycol, TriMethylolPropane(TMP) and hexanodioic acid, m-phthalic acid, phthalic anhydride, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1h at 160 DEG C, then 250 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 150mgKOH/g, acid number is 0.01mgKOH/g, MW is 4000.
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 200 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
The performance detection data of the polyurethane elastomer of the soft that embodiments of the invention 1 ~ embodiment 5 is obtained is in table 1.
Table 1
。
As can be seen from Table 1, the polyurethane elastomer of the soft that embodiments of the invention 1 ~ embodiment 5 is obtained hardness lower than 70A, and tensile strength is high, excellent transparency, and take into account physicals and mechanical property, quality product is good.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.

Claims (8)

1. a polyurethane elastomer for soft, is characterized in that: it is made up of the raw material of following weight part:
Polyester polyol 60-90 part
Vulcabond 10-25 part
Chainextender 3-15 part;
Wherein, the hydroxyl value of polyester polyol is 28 ~ 150mgKOH/g, and acid number is 0.01 ~ 0.3mgK
OH/g, MW are 700 ~ 4000.
2. the polyurethane elastomer of a kind of soft according to claim 1, is characterized in that: it is made up of the raw material of following weight part:
Polyester polyol 70-80 part
Vulcabond 15-20 part
Chainextender 6-12 part.
3. the polyurethane elastomer of a kind of soft according to claim 1, is characterized in that: it is made up of the raw material of following weight part:
Polyester polyol 75 parts
Vulcabond 16 parts
Chainextender 9 parts.
4. the polyurethane elastomer of a kind of soft according to claim 1, it is characterized in that: polyester polyol is by polyprotonic acid, the mixture of any one or both in polynary ester and polyvalent alcohol carry out dealcoholysis and dehydrating polycondensation forms according to the molar ratio of 1:0.9 ~ 1.5 through vacuum fusion method, in vacuum fusion method, first the raw material of above ratio is carried out initial stage esterification 1 ~ 2h at 120 ~ 160 DEG C, then 180 ~ 250 DEG C are warmed up to, in decompression dehydration mode until the hydroxyl value of polyester polyol is for 28 ~ 150mgKOH/g, acid number is 0.01 ~ 0.3mgKOH/g, MW is 700 ~ 4000.
5. the polyurethane elastomer of a kind of soft according to claim 4, is characterized in that: polyvalent alcohol is any one or a few the mixture in glycol ether, butyleneglycol, propylene glycol, hexylene glycol, neopentyl glycol, 2-methyl propanediol, TriMethylolPropane(TMP), glycerine;
Polyprotonic acid is any one or a few the mixture in hexanodioic acid, terephthalic acid, m-phthalic acid;
Polynary ester is phthalic anhydride.
6. the polyurethane elastomer of a kind of soft according to claim 1, is characterized in that: vulcabond comprise 4,4-MDI, 2,4-MDI, extraordinary MDI, IPDI, PPDI, TMXDI, H 12any one or a few mixture in MDI, HDI, XDI, wherein, 4,4-MDI and 2,4-MDI that extraordinary MDI is 3-7 by weight ratio form.
7. the polyurethane elastomer of a kind of soft according to claim 1, it is characterized in that: chainextender is ethylene glycol, propylene glycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2-methyl isophthalic acid, ammediol, hexylene glycol, 3-methyl 1, any one or a few mixture in 5-pentanediol, 1,4 cyclohexane dimethanol.
8. the method for preparing polyurethane elastic body of a kind of soft described in claim 1-7 any one, is characterized in that: it comprises following preparation process:
A, by weight by polyester polyol, vulcabond, chainextender hybrid reaction, the temperature of reaction is 180-250 DEG C, obtained reactant;
B, reactant obtained for step a is added frit reaction in worm press, the temperature of worm press is 140-200 DEG C, granulation under low temperature or normal temperature simultaneously, obtained urethane micelle;
C, urethane micelle, after maturation, obtain polyurethane elastomer.
CN201410506802.XA 2014-09-28 2014-09-28 Low-hardness polyurethane elastomer and preparation method thereof Pending CN104250362A (en)

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